JP2021507505A - Precursor for light absorption layer, manufacturing method of organic-inorganic composite solar cell using this, and organic-inorganic composite solar cell - Google Patents

Abstract

The present specification describes a perovskite precursor; and a precursor for a light absorbing layer containing 0.005 wt% to 0.5 wt% of a fluorine-based organic compound as compared with the perovskite precursor, and an organic-inorganic composite solar cell using the same. Regarding the manufacturing method.

Description

This application is the Korean Patent Application No. 10-2017-0179568 filed with the Korean Intellectual Property Office on December 26, 2017, and the Korean Patent Application No. 10- filed with the Korean Intellectual Property Office on December 7, 2018. Claim the interests of filing date 2018-0156846, all of which are incorporated herein by reference.

The present specification relates to a precursor for a light absorption layer, a method for producing an organic-inorganic composite solar cell using the precursor, and an organic-inorganic composite solar cell.

Research on renewable and clean alternative energy sources such as solar energy, wind power, and hydropower is being actively pursued to solve the global environmental problems caused by the depletion of fossil energy and its use. Of these, interest in solar cells, which directly change electrical energy from sunlight, is increasing significantly. Here, the solar cell means a battery that generates a current-voltage by utilizing the photovoltaic effect of absorbing light energy from sunlight and generating electrons and holes.

The organic-inorganic composite perovskite substance has recently attracted attention as a light absorbing substance of an organic-inorganic composite solar cell because of its high extinction coefficient and the property of being easily synthesized by a solution process.

However, in the case of an organic-inorganic composite solar cell to which an existing perovskite substance is applied, despite its high efficiency, problems such as defects in the light absorption layer and increased resistance during the manufacture of ^{large-area (5 cm 2 or more) devices} There is a problem that the efficiency is reduced compared to the size of the element. In addition, there is a problem that the moisture resistance is weak and a separate sealing technique must be advanced in order to secure long-term stability.

The present specification provides a precursor for a light absorption layer capable of improving coating uniformity when applied to a light absorption layer, and an organic-inorganic composite solar cell using the precursor, while the process is simple. ..

The present specification also provides an organic-inorganic composite solar cell having excellent stability and energy conversion efficiency.

One embodiment of the present specification provides a perovskite precursor; and a precursor for a light absorption layer, which comprises 0.005 wt% to 0.5 wt% of a fluorinated organic compound relative to the perovskite precursor.

Other embodiments herein include the step of preparing a first electrode and
The step of forming the first common layer on the first electrode and
A step of coating the precursor for the light absorption layer on the first common layer to form a light absorption layer,
The step of forming the second common layer on the light absorption layer,
Provided is a method for manufacturing an organic-inorganic composite solar cell, which comprises a step of forming a second electrode on the second common layer.

Yet another embodiment of the present specification provides an organic-inorganic composite solar cell manufactured by the manufacturing method.

Yet another embodiment of the present specification includes a first electrode and
With the first common layer provided on the first electrode,
The light absorption layer provided on the first common layer and
With the second common layer provided on the light absorption layer,
In an organic-inorganic composite solar cell including a second electrode provided on the second common layer,
The light absorption layer contains a compound having a perovskite structure; and a fluorine-based organic compound.
The fluorine-based organic compound provides an organic-inorganic composite solar cell in which 0.005 wt% to 5 wt% of the mass of the light absorption layer is contained.

Since the precursor for a light absorption layer according to one embodiment of the present specification contains a fluorine-based organic compound, there is an effect that the uniformity of coating is increased even if the light absorption layer is formed in a large area.

Further, the method for manufacturing an organic-inorganic composite solar cell according to one embodiment of the present specification can manufacture an organic-inorganic composite solar cell in which the interface characteristics of the light absorption layer are improved and the current density and energy conversion efficiency are improved. There is an advantage.

Further, the method for producing an organic-inorganic composite solar cell according to an embodiment of the present specification absorbs a wide optical spectrum, reduces light energy loss, and improves long-term stability and energy conversion efficiency. It has the advantage of being able to manufacture composite solar cells.

It is a figure which illustrates the structure of the organic-inorganic composite solar cell which concerns on embodiment of this specification. It is a figure which shows the scanning electron microscope (SEM) image of the cross section of the organic-inorganic composite solar cell manufactured in Example 1. FIG. It is a figure which shows the scanning electron microscope (SEM) image of the cross section of the organic-inorganic composite solar cell manufactured in the comparative example 1. FIG. It is a figure which shows the measurement result of the current density corresponding to the voltage of the organic-inorganic composite solar cell which concerns on one Embodiment of this specification. It is a figure which shows the result of having repeatedly measured the current density corresponding to the voltage of the organic-inorganic composite solar cell manufactured in Example 1. It is a figure which shows the result of having repeatedly measured the current density corresponding to the voltage of the organic-inorganic composite solar cell manufactured in the comparative example 1. FIG.

10: 1st electrode 20: 1st common layer 30: Light absorption layer 40: 2nd common layer 50: 2nd electrode

Hereinafter, the present specification will be described in detail.

In the present specification, when a component is referred to as "contains" a component, this means that the other component may be further included rather than excluding the other component unless otherwise specified. To do.

As used herein, when one member is located "above" another member, this is not only when one member is in contact with another, but also between the two members. Including the case where the member of

The precursor for the light absorption layer according to one embodiment of the present specification is a perovskite precursor;

It contains 0.005 wt% to 0.5 wt% of a fluorine-based organic compound as compared with the perovskite precursor.

One embodiment of the present specification has an effect of improving the drive stability of the device without deteriorating the electrical characteristics when the light absorption layer is formed by containing 0.005 wt% to 0.5 wt% of the fluorine-based organic compound. Can be shown.

More specifically, the precursor for the light absorption layer contains a perovskite precursor; and a fluorine-based organic compound of 0.01 wt% to 0.2 wt% with respect to the perovskite precursor.

As used herein, the term "organic compound" means a compound containing a hydrocarbon as a basic skeleton and having a skeleton structure composed of carbon-carbon and carbon-hydrogen covalent bonds. At this time, the skeletal structure may be substituted with other elements.

In the present specification, the "fluorine-based organic compound" means a compound containing fluorine in the main chain of the organic compound.

In one embodiment of the present specification, the fluorine-based organic compound can be used without limitation as long as it is a substance used in the art, and specifically, the main chain is a fluoro group and a perfluoroalkyl (). It can contain at least one of the perfluoro alkyl) groups.

In one embodiment of the specification, the fluorinated organic compound comprises a fluorinated surfactant.

As used herein, the term "surfactant" means a substance having both hydrophilic and hydrophobic moieties in the molecule.

In one embodiment of the present specification, the fluorine-based surfactant can be used without limitation as long as it is a substance used in the art, and specifically, the main chain is a hydrophilic group, a lipophilic group, or a fluoro. It may consist of, but is not limited to, a combination of a (fluoro) group and a perfluoroalkyl group.

In one embodiment of the present specification, the fluorine-based surfactant may be represented by the following chemical formula A.

[Chemical formula A]

In the chemical formula A, x and y are integers of 1 to 10, respectively.

Specifically, as the fluorine-based organic compound, FS-31 manufactured by DuPont, FS-300 manufactured by Zonyl, RS-72-K manufactured by DIC, or FC-4430 manufactured by 3M Corporation can be used.

In one embodiment of the specification, the perovskite precursor comprises an organic halide and a metal halide.

In one embodiment of the specification, the fluorinated organic compound is a fluorinated surfactant.

As used herein, the term "precursor" means a substance at a stage before it becomes a specific substance in a substance metabolism or reaction. For example, the perovskite precursor means a substance in a stage before becoming a perovskite substance, and the precursor for a light absorption layer means a precursor substance for forming a light absorption layer.

In one embodiment of the specification, the organic halide is represented by any one of the following chemical formulas 1-3.

[Chemical formula 1]
R1X1

[Chemical formula 2]
R2 _a R3 _(1-a) X2 _e X3 _(1-e)

[Chemical formula 3]

_{R4 b R5 c R6 d X4 e} 'X5 (1-e')
In the chemical formulas 1 to 3,
R2 and R3 are different from each other
R4, R5 and R6 are different from each other
R1 to R6 are C _n H _{2n + 1} NH ₃ ⁺ , NH ₄ ⁺ , HC (NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ^{+, respectively. _{, CH 3 AsH 3 +, CH}} 3 SbH 3 +, PH 4 +, an _AsH ^{4 +,} and monovalent cation selected from _SbH ^{4 +,}
X1 to X5 are halogen ions that are the same as or different from each other and are independent of each other.
n is an integer of 1-9,
a is a real number with 0 <a <1
b is a real number with 0 <b <1
c is a real number with 0 <c <1
d is a real number with 0 <d <1
b + c + d is 1,
e is a real number with 0 <e <1
e'is a real number with 0 <e'<1.

In one embodiment of the present specification, the R1~R6 each ^{_{C n H 2n + 1 NH 3}} +, NH 4 +, HC (NH 2) 2 +, Cs +, NF 4 +, NCl 4 +, PF 4 + ^{_{, PCl 4 +, CH 3 PH}} 3 +, CH 3 AsH 3 +, PH 4 +, and a monovalent cation selected from _AsH ^{4 +.} More specifically, the R1~R6 each ^{_{C n H 2n + 1 NH 3}} +, HC (NH 2) 2 +, and a monovalent cation selected from Cs ^+.

In one embodiment of the specification, the organic halides are CH ₃ NH ₃ I, HC (NH ₂ ) ₂ I, CH ₃ NH ₃ Br, HC (NH ₂ ) ₂ Br, (CH ₃ NH ₃ ) _a. (HC (NH ₂ ) ₂ ) _(1-a) I _e Br _(1-e) , or (HC (NH ₂ ) ₂ ) _b (CH ₃ NH ₃ ) _c Cs _d I _e Br _(1-e) Yes, a is a real number with 0 <a <1, b is a real number with 0 <b <1, c is a real number with 0 <c <1, d is a real number with 0 <d <1, and b + c + d is 1. , E is a real number with 0 <e <1.

In one embodiment of the specification, the X2 and X3 are different from each other.

In one embodiment of the specification, the X4 and X5 are different from each other.

In one embodiment of the specification, the X1 to X5 are independently I or Br, respectively.

In one embodiment of the specification, the metal halide is represented by the following chemical formula 4.

[Chemical formula 4]
M1X6 ₂

In the chemical formula 4,

M1 is a divalent metal ion selected from ^{Cu 2+} , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ , and Yb ^2+. ,
X6 is a halogen ion.

In one embodiment of the specification, the M1 is Pb ²⁺ .

In one embodiment of the specification, the X6 is I or Br.

In one embodiment of the specification, the metal halide is PbI ₂ or PbBr ₂ .

In one embodiment of the present specification, the precursor for the light absorption layer may be in a solution state. For example, the fluorine-based organic compound, the organic halide, and the metal halide may be dissolved in the solvent.

In one embodiment of the present specification, the solvent is dimethylformamide (DMF), isopropyl alcohol (isopolyl alcohol, IPA), dimethyl sulfoxide (DMSO), gum mabutyrolactone (γ-butyrolactone, BL). -Methylpyrrolidone (n-methylpyrrolidone, NMP), propylene glycol methyl ether (PGME), propylene glycol monomethyl ether acetate (propyllene glycol monomethyl ether acetamide), dimethylacetamide, PGMEA At least one can be included.

One embodiment of the present specification includes a step of preparing a first electrode and
The step of forming the first common layer on the first electrode and
A step of coating the precursor for the light absorption layer on the first common layer to form a light absorption layer,
The step of forming the second common layer on the light absorption layer,
Provided is a method for manufacturing an organic-inorganic composite solar cell, which comprises a step of forming a second electrode on the second common layer.

In one embodiment of the present specification, the steps of coating the precursor for the light absorption layer include a step of coating the precursor for the light absorption layer on the first common layer and the precursor for the coated light absorption layer. It includes the steps of drying, baking, or annealing the body.

In one embodiment of the present specification, the steps of coating the precursor for the light absorbing layer include spin coating, slit coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, brush painting, and the like. Alternatively, a thermal vapor deposition method can be used. Specifically, spin coating can proceed.

In one embodiment of the present specification, the step of drying, baking, or annealing the precursor for the light absorption layer is performed at a temperature of 80 ° C. to 150 ° C. for 10 minutes to 60 minutes. Will be

Specifically, the step of coating the precursor for the light absorption layer is a process of spin-coating the precursor solution for the light absorption layer on the first common layer and then annealing at a temperature of 100 ° C. for 30 minutes. There may be.

One embodiment of the present specification provides an organic-inorganic composite solar cell manufactured by the method for manufacturing an organic-inorganic composite solar cell.

One embodiment of the present specification includes a first electrode and
With the first common layer provided on the first electrode,
The light absorption layer provided on the first common layer and
With the second common layer provided on the light absorption layer,
In an organic-inorganic composite solar cell including a second electrode provided on the second common layer,
The light absorption layer contains a compound having a perovskite structure; and a fluorine-based organic compound.
The fluorine-based organic compound provides an organic-inorganic composite solar cell in which 0.005 wt% to 5 wt% of the mass of the light absorption layer is contained.

In the organic-inorganic composite solar cell, the fluorine-based organic compound is the same as that described above in the production method.

FIG. 1 shows the structure of an organic-inorganic composite solar cell according to an embodiment of the present specification. Specifically, FIG. 1 shows an organic-inorganic composite solar cell in which a first electrode 10, a first common layer 20, a light absorption layer 30, a second common layer 40, and a second electrode 50 are sequentially laminated. Indicated.

The organic-inorganic composite solar cell according to the present specification is not limited to the laminated structure of FIG. 1, and may further include additional members.

In one embodiment of the present specification, the compound having a perovskite structure is represented by any one of the following chemical formulas 5 to 7.

[Chemical formula 5]
R1M1X1 ₃

[Chemical formula 6]
R2 _a R3 _(1-a) M2X2 _z X3 _(3-z)

[Chemical formula 7]
_{R4 b R5 c R6 d M3X4 z} 'X5 (3-z')

In the chemical formulas 5 to 7,
R2 and R3 are different from each other
R4, R5 and R6 are different from each other
R1 to R6 are C _n H _{2n + 1} NH ₃ ⁺ , NH ₄ ⁺ , HC (NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ^{+, respectively. _{, CH 3 AsH 3 +, CH}} 3 SbH 3 +, PH 4 +, an _AsH ^{4 +,} and monovalent cation selected from _SbH ^{4 +,}
M1 to M3 are the same as or different from each other, and independently of each other, Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Bi ²⁺ , Pb ^2+. , And a divalent metal ion selected from ^{Yb 2+,}
X1 to X5 are halogen ions that are the same as or different from each other and are independent of each other.
n is an integer of 1-9,
a is a real number with 0 <a <1
b is a real number with 0 <b <1
c is a real number with 0 <c <1
d is a real number with 0 <d <1
b + c + d is 1,
z is a real number with 0 <z <3,
z'is a real number with 0 <z'<3.

In one embodiment of the present specification, the compound having a perovskite structure in the light absorption layer can contain a single cation. In the present specification, a single cation means a cation using one kind of monovalent cation. That is, in the chemical formula 5, it means that only one kind of monovalent cation is selected as R1. For example, R1 of Formula _{5, C n H 2n + 1 NH} 3 is ^+, n may be an integer of 1 to 9.

In one embodiment of the present specification, the compound having a perovskite structure in the light absorption layer may contain a complex cation. In the present specification, the complex cation means a compound cation using two or more kinds of monovalent cations. That is, in Chemical Formula 6, monovalent cations in which R2 and R3 are different from each other are selected, and in Chemical Formula 7, monovalent cations in which R4 to R6 are different from each other are selected. For example, R2 of Formula _{6, + C n H 2n + 1} NH 3, R3 is, HC _{(NH 2)} may be a ^{2 +.} Further, R4 of Formula _{7, + C n H 2n + 1} NH 3, R5 ^{_{is, + HC (NH 2) 2}} , R6 may be a Cs ^+.

In one embodiment of the specification, the compound having a perovskite structure is represented by Chemical Formula 5.

In one embodiment of the specification, the compound having a perovskite structure is represented by Chemical Formula 6.

In one embodiment of the specification, the compound having a perovskite structure is represented by Chemical Formula 7.

In one embodiment of the present specification, the R1~R6 each ^{_{C n H 2n + 1 NH 3}} +, HC (NH 2) 2 +, or Cs ^+. At this time, R2 and R3 are different from each other, and R4 to R6 are different from each other.

In one embodiment of the present specification, the R1 ^{_{is, CH 3 NH 3 +, HC}} (NH 2) 2 +, or Cs ^+.

In one embodiment of the present specification, the R2 and R4 are each _CH ³ _NH 3 ^+.

In one embodiment of the present specification, the R3 and R5 are each HC _{(NH 2)} is a ^{2 +.}

In one embodiment of the specification, the R6 is Cs ⁺ .

In one embodiment of the specification, the M1 to M3 are Pb ²⁺ , respectively.

In one embodiment of the specification, the X2 and X3 are different from each other.

In one embodiment of the specification, the X4 and X5 are different from each other.

In one embodiment of the specification, the X1 to X5 are F or Br, respectively.

In one embodiment of the specification, a is a real number of 0 <a <1 because the sum of R2 and R3 is 1. Further, since the sum of X2 and X3 is 3, z is a real number of 0 <z <3.

In one embodiment of the present specification, b is a real number of 0 <b <1 and c is a real number of 0 <c <1 because the sum of R4, R5 and R6 is 1. d is a real number of 0 <d <1, and b + c + d is 1. Further, since the sum of X4 and X5 is 3, z'is a real number of 0 <z'<3.

In one embodiment of the specification, the compound having a perovskite structure is CH ₃ NH ₃ PbI ₃ , HC (NH ₂ ) ₂ PbI ₃ , CH ₃ NH ₃ PbBr ₃ , HC (NH ₂ ) ₂ PbBr ₃ , (CH). _{3 NH 3) a (HC (} NH 2) 2) (1-a) PbI z Br (3-z), or _{(HC (NH 2) 2)} b (CH 3 NH 3) c Cs d PbI z 'Br _(3-z') , where a is a real number of 0 <a <1, b is a real number of 0 <b <1, c is a real number of 0 <c <1, and d is 0 <d <1. , B + c + d is 1, z is a real number of 0 <z <3, and z'is a real number of 0 <z'<3.

In one embodiment of the present specification, the light absorption layer contains a fluorine-based organic compound in an amount of 0.005 wt% to 5 wt% based on the mass of the light absorption layer. Specifically, the light absorption layer contains a fluorine-based organic compound in an amount of 0.005 wt% to 3 wt% based on the mass of the light absorption layer. More specifically, the light absorption layer contains a fluorine-based organic compound in an amount of 0.005 wt% to 1 wt% based on the mass of the light absorption layer. More specifically, the light absorption layer contains a fluorine-based organic compound in an amount of 0.005 wt% to 0.5 wt% based on the mass of the light absorption layer.

The content range of the fluorine-based organic compound relative to the mass of the light absorption layer is the content range produced by using the organic compound in the above-mentioned range in the precursor for the light absorption layer. That is, when the precursor for the light absorption layer contains a fluorine-based organic compound of 0.005 wt% to 0.5 wt% with respect to the perovskite precursor, the light absorption layer formed by using the precursor for the light absorption layer. The organic compound is contained in an amount of 0.005 wt% to 5 wt% based on the mass of the light absorption layer.

In one embodiment of the present specification, the content of the organic compound contained in the light absorption layer can be measured by a method used in the art. For example, mass spectrometry methods such as LCMS (Liquid Chromatography coupled to Mass Spectrometry) or GCMS (Gas Chromatography coupled to Mass Spectrometry); HPLC (High-performance) Is.

In the present specification, the first common layer and the second common layer mean an electron transport layer or a hole transport layer, respectively. At this time, the first common layer and the second common layer are not the same layer as each other. For example, when the first common layer is an electron transport layer, the second common layer is a hole transport layer. When the first common layer is a hole transport layer, the second common layer is an electron transport layer.

In one embodiment of the present specification, the organic-inorganic composite solar cell may additionally include a substrate under the first electrode.

In one embodiment of the present specification, as the substrate, a substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness can be used. Specifically, a glass substrate, a thin film glass substrate, or a plastic substrate can be used. The plastic substrate is made of a single layer of a flexible film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (polyetheretherketone), and polyimide (polyimide). Included in form. However, the substrate is not limited to this, and a substrate usually used for an organic-inorganic composite solar cell can be used.

In the present specification, the first electrode may be an anode and the second electrode may be a cathode. Further, the first electrode may be a cathode, and the second electrode may be an anode.

In one embodiment of the present specification, the first electrode may be a transparent electrode, and the organic-inorganic composite solar cell may absorb light via the first electrode.

In one embodiment of the present specification, when the first electrode is a transparent electrode, the first electrode is made of a glass and a quartz plate, as well as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). , Polypropylene (polypolylane, PP), polyimide (polyimide, PI), polycarbonate (polycarbornate, PC), polystyrene (polystylelene, PS), polyoxyethylene (polyoxyethrene, POM), AS resin (acrylonilile style resin) Used when a conductive substance is doped onto a flexible and transparent substance such as plastic containing butadiene style polymer, triacetyl cellulose (TAC), and polypropylene (PAR). it can. Specifically, the first electrode is composed of indium tin oxide (ITO), fluorine-topped tin oxide (FTO), aluminum-doped zinc oxide (AZO), and the like. It may be IZO (indium zinc oxide), ZnO-Ga ₂ O ₃ , ZnOAl ₂ O ₃ , and ATO (antimony tin oxide), and more specifically, the first electrode is ITO. May be good.

In one embodiment of the present specification, the first electrode may be a translucent electrode. When the first electrode is a translucent electrode, it can be made of a metal such as silver (Ag), gold (Au), magnesium (Mg), or an alloy thereof.

In one embodiment of the present specification, the second electrode may be a metal electrode. Specifically, the metal electrodes include silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and the like. It can contain one or more selected from the group consisting of palladium (Pd), magnesium (Mg), chromium (Cr), calcium (Ca), and sumalium (Sm).

In one embodiment of the present specification, the organic-inorganic composite solar cell may have a n-ip structure. When the organic-inorganic composite solar cell according to the present specification has an n-ip structure, the second electrode may be a metal electrode, an oxide / metal composite electrode, or a carbon electrode. Specifically, the second metal is gold (Au), silver (Ag), aluminum (Al), MoO ₃ / Au, MoO ₃ / Ag, MoO ₃ / Al, V ₂ O ₅ / Au, V ₂ O. It can include ₅ / Ag, V ₂ O ₅ / Al, WO ₃ / Au, WO ₃ / Ag, or WO _{3 / Al.}

In the present specification, the n-ip structure means a structure in which a first electrode, an electron transport layer, a light absorption layer, a hole transport layer, and a second electrode are sequentially laminated.

In one embodiment of the present specification, the organic-inorganic composite solar cell may have a p-in structure. When the organic-inorganic composite solar cell according to the present specification has a p-in structure, the second electrode may be a metal electrode.

In the present specification, the p-in structure means a structure in which a first electrode, a hole transport layer, a light absorption layer, an electron transport layer, and a second electrode are sequentially laminated.

In the present specification, the hole transport layer and / or electron transport layer material is a substance that increases the probability that the generated charge is transferred to the electrode by efficiently transmitting electrons and holes to the light absorption layer. It may be, but there is no particular limitation.

In one embodiment of the present specification, the electron transport layer may contain a metal oxide. Specific examples of the metal oxide include Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, and Sr oxide. One of Yr oxide, La oxide, V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, Ta oxide, and SrTi oxide, and composites thereof. Alternatively, two or more selected ones can be used. Specifically, it _{may be TiO 2} , but it is not limited to this.

In one embodiment of the present specification, the electron transport layer can improve the charge characteristics by utilizing doping, and the surface can be modified by using a fullerene derivative or the like.

In one embodiment of the specification, the electron transport layer is coated on one surface of a first electrode using sputtering, E-Bam, thermal deposition, spin coating, screen printing, inkjet printing, doctor blades, or gravure printing. It is formed by being coated or coated in a film form.

In one embodiment of the present specification, the hole transport layer may be an anode buffer layer.

In one embodiment of the specification, the hole transport layer is introduced by methods such as spin coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, gravure coating, brush painting, thermal deposition and the like. It is possible.

In one embodiment of the specification, the hole transport layer is tertiary butyl pyridine (tBP), lithium bis (trifluoromethanesulfonyl) imide (Lithium Bis (Trifluoromethanesulfonyl) Ide, LiTFSI), poly (liTFSI). 3,4-Ethylenedioxythiophene): Poly (4-styrenesulfonate) (PEDOT: PSS), 2,2', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) -9, Although 9'-spirobifluorene (2,2', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) -9,9'-spirobifluorene, Spiro-OMeTAD) and the like can be used, It is not limited to these.

Hereinafter, in order to specifically explain the present specification, examples will be given and described in detail. However, the examples according to the present specification can be transformed into various different forms, and the scope of the present specification is not construed as being limited to the examples described below. The examples herein are provided to provide a more complete description of the specification to those with average knowledge in the art.

Example 1.

_{A solution containing 2 wt% titanium dioxide (TiO 2} ) in isopropyl alcohol (isopropanol alcohol) was spin-coated on a non-alkali glass substrate on which indium tin oxide (ITO) was sputtered at 2,000 rpm, and then 150 ° C. Was heated for 30 minutes. After that, perovskite ((HC (NH ₂ ) ₂ ) _x (CH ₃ NH ₃ ) _y Cs _1-x-y PbI _z Br _3-z (0 <x <1, 0 <y <1, 0.8 <x + y) <1,0 <z <3)) A solution prepared by dissolving a precursor and a fluorine-based organic compound (FC-4430) having a ratio of perobskite precursor of 0.05 wt% in dimethylformamide was dissolved at 5,000 rpm. After spin coating with, it was dried at 100 ° C. for 30 minutes to form a light absorbing layer. Then, Spiro-OMeTAD was dissolved in chlorobenzene, and then a solution containing tertiary butylpyridine (tBP) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) was spin-coated, and then Ag was vacuum-deposited. ..

FIG. 2 shows a scanning electron microscope (SEM) image of the cross section of the organic-inorganic composite solar cell manufactured in Example 1. From FIG. 2, it can be confirmed that the organic-inorganic composite solar cell manufactured according to the embodiment of the present specification has no pores in the light absorption layer, the surface of the light absorption layer is uniform, and the crystal size is increased. ..

Comparative example 1.

_{A solution containing 2} wt% of TiO 2 in isopropyl alcohol was spin-coated on a non-alkali glass substrate sputtered with indium tin oxide (ITO) at 2,000 rpm, and then heated at 150 ° C. for 30 minutes. After that, perovskite ((HC (NH ₂ ) ₂ ) _x (CH ₃ NH ₃ ) _y Cs _1-x-y PbI _z Br _3-z (0 <x <1, 0 <y <1, 0.8 <x + y) <1,0 <z <3)) A solution in which the precursor was dissolved in dimethylformamide was spin-coated at 5,000 rpm and then dried at 100 ° C. for 30 minutes to form a light absorbing layer. Then, Spiro-OMeTAD was dissolved in chlorobenzene, a solution containing tBP and LiTFSI was spin-coated, and then Ag was vacuum-deposited.

FIG. 3 shows a scanning electron microscope (SEM) image of the cross section of the organic-inorganic composite solar cell manufactured in Comparative Example 1. From FIG. 3, in the case of the organic-inorganic composite solar cell manufactured in Comparative Example 1, the cross section of the light absorption layer has more pores, the surface of the light absorption layer is rough, and the crystal size is smaller than in Example 1. You can check.

Comparative example 2.

_{A solution containing 2} wt% of TiO 2 in isopropyl alcohol was spin-coated on a non-alkali glass substrate sputtered with indium tin oxide (ITO) at 2,000 rpm, and then heated at 150 ° C. for 30 minutes. After that, perovskite ((HC (NH ₂ ) ₂ ) _x (CH ₃ NH ₃ ) _y Cs _1-x-y PbI _z Br _3-z (0 <x <1, 0 <y <1, 0.8 <x + y) <1,0 <z <3)) A solution prepared by dissolving a precursor and a fluoroorganic compound (FC-4430) with a ratio of perovskite precursor of 0.55 wt% in dimethylformamide (dimformamide) at 5,000 rpm. After spin coating with, it was dried at 100 ° C. for 30 minutes to form a light absorbing layer. Then, Spiro-OMeTAD was dissolved in chlorobenzene, a solution containing tBP and LiTFSI was spin-coated, and then Ag was vacuum-deposited.

Comparative example 3.

_{A solution containing 2} wt% of TiO 2 in isopropyl alcohol was spin-coated on a non-alkali glass substrate on which indium tin oxide (ITO) was sputtered at 2,000 rpm, and then heated at 150 ° C. for 30 minutes. did. After that, perovskite ((HC (NH ₂ ) ₂ ) _x (CH ₃ NH ₃ ) _y Cs _1-x-y PbI _z Br _3-z (0 <x <1, 0 <y <1, 0.8 <x + y) A solution of <1,0 <z <3) precursor and sodium lauryl sulfate in 0.05 wt% of perovskite precursor in dimethylformamide was spin-coated at 5,000 rpm and then spin-coated at 100 ° C. for 30 minutes. It was dried to form a light absorbing layer. After that, Spiro-OMeTAD was dissolved in chlorobenzene, a solution containing tBP and LiTFSI was spin-coated, and then Ag was vacuum-deposited.

Table 1 shows the performance of the organic-inorganic composite solar cell according to the embodiment of the present specification.

In Table 1, _Voc stands for open circuit voltage, J _sc stands for short-circuit current, FF stands for Fill factor, and PCE stands for energy conversion efficiency. The open circuit voltage and the short circuit current are the X-axis and Y-axis intercepts in the four quadrants of the voltage-current density curve, respectively, and the higher these two values, the higher the efficiency of the solar cell. The Fill factor is a value obtained by dividing the maximum width of a rectangle that can be drawn inside a curve by the product of a short-circuit current and an open circuit voltage. The energy conversion efficiency is obtained by dividing these three values by the intensity of the irradiated light, and the higher the value, the more preferable.

From Table 1 above, it can be confirmed that the performance of the device deteriorates when the fluorine-based organic compound is not contained (Comparative Example 1) or when the fluorine-based organic compound is contained in excess of 0.5 wt% (Comparative Example 2). it can. Further, it was confirmed that when another surfactant other than the fluorine-based organic compound was used (Comparative Example 3), it was impossible to manufacture a normal device.

FIG. 4 shows the measurement results of the current density according to the voltage of the organic-inorganic composite solar cell according to the embodiment of the present specification.

The stability of the device was measured using a Keithley 2420 source meter using the organic-inorganic composite solar cells manufactured in Example 1 and Comparative Example 1 as a light source using an ABET Sun 3000 solar simulator. At the time of one measurement, the current is measured after applying a voltage while decreasing from 1.2V to 0V by 12mV per 0.1 seconds, and at the time of 10 consecutive measurements, the waiting time between measurements is 1 minute in a dark room. Met.

FIG. 5 shows the results of repeated measurement of the current density according to the voltage of the organic-inorganic composite solar cell manufactured in Example 1. In FIG. 5, the 1st sweep indicates the first measurement result, and the 2nd to 4th are the results of sequentially measuring from the second measurement result to the fourth measurement result. From FIG. 5, it can be confirmed that the performance of the element is maintained even if the organic-inorganic composite solar cell manufactured according to the embodiment of the present specification is repeatedly measured four times. That is, when a fluorine-based organic compound is contained in forming the light absorption layer, it can be confirmed that the produced organic-inorganic composite solar cell is excellent in stability.

FIG. 6 shows the results of repeated measurement of the current density according to the voltage of the organic-inorganic composite solar cell manufactured in Comparative Example 1. From FIG. 6, in the case of the organic-inorganic composite solar cell manufactured in the comparative example, it can be confirmed that the performance of the element is deteriorated even if the measurement is performed only twice (2nd sweep in FIG. 6). That is, it can be confirmed that the stability of the produced organic-inorganic composite solar cell is lowered when the fluorine-based organic compound is not contained in forming the light absorption layer.

Claims (10)

A precursor for a light absorption layer containing a perovskite precursor; and a fluorine-based organic compound in an amount of 0.005 wt% to 0.5 wt% with respect to the perovskite precursor. The perovskite precursor comprises an organic halide and a metal halide.
The precursor for a light absorption layer according to claim 1. The organic halide is represented by any one of the following chemical formulas 1 to 3.
The precursor for a light absorption layer according to claim 2:
[Chemical formula 1]
R1X1
[Chemical formula 2]
R2 _a R3 _(1-a) X2 _e X3 _(1-e)
[Chemical formula 3]
_{R4 b R5 c R6 d X4 e} 'X5 (1-e')
In the chemical formulas 1 to 3,
R2 and R3 are different from each other
R4, R5 and R6 are different from each other
R1 to R6 are C _n H _{2n + 1} NH ₃ ⁺ , NH ₄ ⁺ , HC (NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ^{+, respectively. _{, CH 3 AsH 3 +, CH}} 3 SbH 3 +, PH 4 +, an _AsH ^{4 +,} and monovalent cation selected from _SbH ^{4 +,}
X1 to X5 are halogen ions that are the same as or different from each other and are independent of each other.
n is an integer of 1-9,
a is a real number with 0 <a <1
b is a real number with 0 <b <1
c is a real number with 0 <c <1
d is a real number with 0 <d <1
b + c + d is 1,
e is a real number with 0 <e <1
e'is a real number with 0 <e'<1. The metal halide is represented by the following chemical formula 4.
The precursor for a light absorption layer according to claim 2:
[Chemical formula 4]
M1X6 ₂
In the chemical formula 4,
M1 is a divalent metal ion selected from ^{Cu 2+} , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ , and Yb ^2+. ,
X6 is a halogen ion. The fluorine-based organic compound contains a fluorine-based surfactant.
The precursor for a light absorption layer according to any one of claims 1 to 4. Steps to prepare the first electrode and
The step of forming the first common layer on the first electrode and
A step of coating the precursor for a light absorption layer according to any one of claims 1 to 5 on the first common layer to form a light absorption layer.
The step of forming the second common layer on the light absorption layer,
A method for manufacturing an organic-inorganic composite solar cell, which comprises a step of forming a second electrode on the second common layer. An organic-inorganic composite solar cell manufactured by the method for manufacturing an organic-inorganic composite solar cell according to claim 6. With the first electrode
With the first common layer provided on the first electrode,
The light absorption layer provided on the first common layer and
With the second common layer provided on the light absorption layer,
In an organic-inorganic composite solar cell including a second electrode provided on the second common layer,
The light absorption layer contains a compound having a perovskite structure; and a fluorine-based organic compound.
The fluorine-based organic compound is an organic-inorganic composite solar cell containing 0.005 wt% to 5 wt% of the mass of the light absorption layer. The compound having a perovskite structure is represented by any one of the following chemical formulas 5 to 7.
The organic-inorganic composite solar cell according to claim 8.
[Chemical formula 5]
R1M1X1 ₃
[Chemical formula 6]
R2 _a R3 _(1-a) M2X2 _z X3 _(3-z)
[Chemical formula 7]
_{R4 b R5 c R6 d M3X4 z} 'X5 (3-z')
In the chemical formulas 5 to 7,
R2 and R3 are different from each other
R4, R5 and R6 are different from each other
R1 to R6 are C _n H _{2n + 1} NH ₃ ⁺ , NH ₄ ⁺ , HC (NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ^{+, respectively. _{, CH 3 AsH 3 +, CH}} 3 SbH 3 +, PH 4 +, an _AsH ^{4 +,} and monovalent cation selected from _SbH ^{4 +,}
M1 to M3 are the same as or different from each other, and independently of each other, Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Bi ²⁺ , Pb ^2+. , And a divalent metal ion selected from ^{Yb 2+,}
X1 to X5 are halogen ions that are the same as or different from each other and are independent of each other.
n is an integer of 1-9,
a is a real number with 0 <a <1
b is a real number with 0 <b <1
c is a real number with 0 <c <1
d is a real number with 0 <d <1
b + c + d is 1,
z is a real number with 0 <z <3,
z'is a real number with 0 <z'<3. The fluorine-based organic compound contains a fluorine-based surfactant.
The organic-inorganic composite solar cell according to claim 8 or 9.